The present invention relates to cosmetics containing partially dissolved crystalline vitamin B3 compounds.
Niacin, also known as vitamin B3, is the common name for nicotinic acid. The physiologically active form of niacin is niacinamide, also a member of the vitamin B3 family of compounds. Niacin and niacinamide (nicotinic acid amide) function in the body as components of two coenzymes: nicotinamide adenine dinucleotide (NAD) and nicotinamide adenine dinucleotide phosphate (NADP). Until recently, these vitamin B3 compounds were used exclusively to treat niacin deficiency and pellegra.
Today, however, vitamin B3 compounds have also found use in the area of skin care actives. British Patent 1,370,236 describes compositions for skin lightening containing 0.5% to 10% niacin. Similarly, U.S. Pat. No. 4,096,240 discloses the use of 0.1% to 10% niacinamide for skin lightening. Vitamin B3 compounds have also been found useful in regulating the texture of human skin. See PCT application WO 97/39733, to Oblong et al.
However, when topically applied to the skin, only about 2-4% of the applied vitamin B3 compound actually penetrates into the skin. Thus, there exists a need for cosmetic compositions comprising vitamin B3 compounds which provide improved skin penetration of vitamin B3 compounds. The present inventors have discovered that cosmetic compositions which incorporate vitamin B3 compounds in a polar solvent such that the vitamin B3 compound exceeds the saturation solubility of the polar solvent improves the overall skin penetration of the vitamin B3 compound.
It is, therefore, an aspect of the present invention to provide cosmetic compositions which enhance the amount of topically applied vitamin B3 compounds which penetrates the skin.
Another aspect of the present invention is to provide cosmetic compositions comprising a polar solvent and vitamin B3 compounds as undissolved crystals.
A further aspect of the present invention is to provide lipstick compositions comprising a polar solvent and vitamin B3 compounds as undissolved crystals.
These and other aspects will become readily apparent from the detailed description which follows.
The present invention relates to cosmetic compositions, comprising:
a.) from about 0.1% to about 50%, by weight, of vitamin B3 compound;
b.) from about 0% to about 90%, by weight, of an emollient component comprising from 0% to about 100%, by weight, of an oil liquid at ambient temperature;
c.) from about 0.01% to about 80%, by weight, of a polar solvent;
d.) from about 0% to about 30%, by weight of a surfactant;
e.) from about 0% to about 90%, by weight, of a solidifying agent; and
f.) from about 0% to about 90%, by weight, of a color
wherein the vitamin B3 compound is added to the composition such that the concentration of the vitamin B3 compound exceeds the saturation solubility of the vitamin B3 compound in the composition.
All percentages, parts and ratios are based upon the total weight of the cosmetic compositions of the present invention, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and, therefore, do not include carriers or by-products that may be included in commercially available materials, unless otherwise specified.
As used herein the term xe2x80x9ccomprisingxe2x80x9d means that the composition can contain other ingredients which are compatible with the composition and which preferably do not substantially disrupt the compositions of the present invention. The term encompasses the terms xe2x80x9cconsisting ofxe2x80x9d and xe2x80x9cconsisting essentially ofxe2x80x9d.
As used herein, the term xe2x80x9ccosmeticsxe2x80x9d includes make-up, foundation, and skin care products. The term xe2x80x9cmake-upxe2x80x9d refers to products that leave color on the face, including foundation, blacks and browns, i.e., mascara, concealers, eye liners, brow colors, eye shadows, blushers, lip colors, and so forth. Skin care products are those used to treat or care for, or somehow moisturize, improve, or clean the skin. Products contemplated by the phrase xe2x80x9cskin care productsxe2x80x9d include, but are not limited to, adhesives, bandages, toothpaste, anhydrous occlusive moisturizers, antiperspirants, deodorants, powder laundry detergent, fabric softener towels, occlusive drug delivery patches, nail polish, powders, tissues, wipes, solid emulsion compact, hair conditioners-anhydrous and the like. The term xe2x80x9cfoundationxe2x80x9d refers to liquid, creme, mousse, pancake, compact, concealer or like product created or reintroduced by cosmetic companies to even out the overall coloring of the skin. Foundation is manufactured to work better over moisturized and/or oiled skin.
Vitamin B3 Component
The compositions of the present invention comprise a safe and effective amount of a natural or synthetic vitamin B3 compound. The compositions of the present invention preferably comprise from above 0.01% to about 50%, more preferably from about 0.1% to about 30%, even more preferably 0.5% to about 20%, most preferably from about 1% to about 10% of the vitamin B3 compound.
As used herein, xe2x80x9cvitamin B3 compoundxe2x80x9d means a compound having the formula: 
wherein R is xe2x80x94CONH2 (i.e., niacinamide), xe2x80x94COOH (i.e., nicotinic acid) or xe2x80x94CH2OH (i.e., nicotinyl alcohol); derivatives thereof; and salts of any of the foregoing.
Exemplary derivatives of the foregoing vitamin B3 compounds include nicotinic acid esters, including non-vasodilating esters of nicotinic acid, nicotinyl amino acids, nicotinyl alcohol esters of carboxylic acids, nicotinic acid N-oxide and niacinamide N-oxide.
Suitable esters of nicotinic acid include nicotinic acid esters of C1-C22, preferably C1-C16, more preferably C1-C6 alcohols. The alcohols are suitably straight-chain or branched chain, cyclic or acyclic, saturated or unsaturated (including aromatic), and substituted or unsubstituted. The esters are preferably non-rubifacient. As used herein, xe2x80x9cnon-rubifacientxe2x80x9d means that the ester does not commonly yield a visible flushing response after application to the skin in the subject compositions (the majority of the general population would not experience a visible flushing response, although such compounds may cause vasodilation not visible to the naked eye). Alternatively, a nicotinic acid material which is rubifacient at higher doses could be used at a lower dose to reduce the rubifacient effect. Non-rubifacient esters of nicotinic acid include tocopherol nicotinate and inositol hexanicotinate; tocopherol nicotinate is preferred.
Other derivatives of the vitamin B3 compound are derivatives of niacinamide resulting from substitution of one or more of the amide group hydrogens. Nonlimiting examples of derivatives of niacinamide useful herein include nicotinyl amino acids, derived, for example, from the reaction of an activated nicotinic acid compound (e.g. nicotinic acid azide or nicotinyl chloride) with an amino acid, and nicotinyl alcohol esters of organic carboxylic acids (e.g. C1-C18). Specific examples of such derivatives include; nicotinuric acid and nicotinyl hydroxamic acid, which have the following chemical structures:
nicotinuric acid: 
nicotinyl hydroxamic acid: 
Exemplary nicotinyl alcohol esters include nicotinyl alcohol esters of the carboxylic acids salicylic acid, acetic acid, glycolic acid, palmitic acid and the like. Other non-limiting examples of vitamin B3 compounds useful herein are 2-chloronicotinamide, 6-aminonicotinamide, 6-methylnicotinamide, n-methyl-nicotinamide, n,n-diethylnicotinamide, n-(hydroxymethyl)-nicotinamide, quinolinic acid imide, nicotinanilide, n-benzylnicotinamide, n-ethylnicotinamide, nifenazone, nicotinaldehyde, isonicotinic acid, methyl isonicotinic acid, thionicotinamide, nialamide, 1-(3-pyridylmethyl) urea, 2-mercaptonicotinic acid, nicomol, and niaprazine.
Examples of the above vitamin B3 compounds are well known in the art and are commercially available from a number of sources, e.g., the Sigma Chemical Componay (St. Louis, Mo.); ICN Biomedicals. Inc. (Irvin, Calif.) and Aldrich Chemical Company (Milwaukee, Wis.).
One or more vitamin B3 compounds may be used herein. Preferred vitamin B3 compounds are niacinamide and tocopherol nicotinate. Niacinamide is more preferred.
When used, salts, derivatives, and salt derivatives of niacinamide are preferably those having substantially the same efficacy as niacinamide in the methods of regulating skin condition described herein.
Salts of the vitamin B3 compound are also useful herein. Nonlimiting examples of salts of the vitamin B3 compound useful herein include organic or inorganic salts, such as inorganic salts with anionic inorganic species (e.g., chloride, bromide, iodide, carbonate, preferably chloride), and organic carboxylic acid salts (including mono-, di- and tri-C1-C18 carboxylic acid salts, e.g., acetate, salicylate, glycolate, lactate, malate, citrate, preferably monocarboxylic acid salts such as acetate). These and other salts of the vitamin B3 compound can be readily prepared by the skilled artisan, for example, as described by W. Wenner, xe2x80x9cThe Reaction of L-Ascorbic and D-Isoascorbic Acid with Nicotinic Acid and Its Amidexe2x80x9d. J. Organic Chemistry, VOL. 14, 22-26 (1949), which is incorporated herein by reference. Wenner describes the synthesis of the ascorbic acid salt of niacinamide.
In a preferred embodiment, the ring nitrogen of the vitamin B3 compound is substantially chemically free (e.g., unbound and/or unhindered), or after delivery to the skin becomes substantially chemically free (xe2x80x9cchemically freexe2x80x9d is hereinafter alternatively referred to as xe2x80x9cuncomplexedxe2x80x9d). More preferably, the vitamin B3 compound is essentially uncomplexed. Therefore, if the composition contains the vitamin B3 compound in a salt or otherwise complexed form, such complex is preferably substantially reversible, more preferably essentially reversible, upon delivery of the composition to the skin. For example, such complex should be substantially reversible at a pH of from about 5.0 to about 6.0. Such reversibility can be readily determined by one having ordinary skill in the art.
More preferably the vitamin B3 compound is substantially uncomplexed in the composition prior to delivery to the skin. Exemplary approaches to minimizing or preventing the formation of undesirable complexes include omission of materials which form substantially irreversible or other complexes with the vitamin B3 compound, pH adjustment, ionic strength adjustment, the use of surfactants, and formulating wherein the vitamin B3 compound and materials which complex therewith are in different phases. Such approaches are well within the level of ordinary skill in the art.
Thus, in a preferred embodiment, the vitamin B3 compound contains a limited amount of the salt form and is more preferably substantially free of salts of a vitamin B3 compound. Preferably the vitamin B3 compound contains less than about 50% of such salt, and is more preferably essentially free of the salt form. The vitamin B3 compound in the compositions hereof having a pH of from about 4 to about 7 typically contain less than about 50% of the salt form.
The vitamin B3 compound may be included as the substantially pure material, or as an extract obtained by suitable physical and/or chemical isolation from natural (e.g., plant) sources. The vitamin B3 compound is preferably substantially pure more preferably essentially pure.
The cosmetic compositions of the present invention comprise the vitamin B3 compounds and the polar solvent at concentrations such that the concentration of the vitamin B3 compound exceeds the saturation solubility (at ambient temperature; say, at about 20xc2x0 C.) of the vitamin B3 compound in the composition. As a result, a portion of the vitamin B3 compound is present in undissolved form. Preferably, the concentration of the vitamin B3 compound will be at least 50% greater than the saturation solubility at ambient temperature, more preferably at least 100% greater than the saturation solubility at ambient temperature and most preferably at least 150% greater or more than the saturation solubility at ambient temperature of the vitamin B3 compound in the composition.
Polar Solvent
Solvents suitable for use in the present invention include any polar solvent capable of dissolving the vitamin B3 compound. Suitable polar solvents include: water; alcohols, such as ethanol, propyl alcohol, isopropyl alcohol, hexanol, and benzyl alcohol; polyols, such as propylene glycol, polypropylene glycol, bulylene glycol, hexylene glycol, maltitol, sorbitol, and glycerine; panthenol dissolved in glycerine, flavor oils, and mixtures thereof. Mixtures of these solvents can also be used. Preferred polar solvents are polyhydric alcohols and water. Examples of preferred solvents include glycerine, panthenol in glycerine, glycols such as propylene glycol and butylene glycol, polyethylene glycols, water and mixtures thereof. The most preferred polar solvents for use are alcohols, glycerine, panthenol, propylene glycol, butylene glycol hexylene glycol and mixtures thereof.
Typically, the cosmetic compositions of the present invention will comprise from about 0.1% to about 80%, preferably from about 0.5% to about 60%, more preferably from about 1% to about 30% and most preferably from about 3% to about 18% polar solvent.
Emollient Component
Also essential to the compositions of the present invention is an emollient component. The emollient component can comprise fats, oils, fatty alcohols, fatty acids and esters which aid application and adhesion, yield gloss and most importantly provide occlusive moisturization.
Suitable emollients for use are isostearic acid derivatives, isopropyl palmitate, lanolin oil, diisopropyl dimerate, maleated soybean oil, octyl palmitate, isopropyl isostearate, cetyl lactate, cetyl ricinolcate, tocopheryl acetate, acetylated lanolin alcohol, cetyl acetate, phenyl trimethicone, glyceryl oleate, tocopherol linoelate, wheat germ glycerides, aracidyl propionate, myristyl lactate, decyl oleate, propylene glycol ricinoleate, isopropyl lanolate, pentaerythrityl tetrastearate, neopentylglycol dicapnlate/dicaprate, hydrogenated coco-glycerides, isononyl isononanoate, isotridecyl isononanoate, myristal myristate, triisocetyl citrate, cetyl alcohol, octyl dodecanol, oleyl alcohol, panthenol, lanolin alcohol, linoleic acid, linolenic acid, sucrose esters of fatty acids, octyl hydroxystearate and mixtures thereof. Examples of other suitable emollients can be found in the Cosmetic Bench Reference, pp. 1.19-1.22 (1996).
Particularly preferred emollients are polar emollient emulsifiers such as linear or branched chained polyglycerol esters. By xe2x80x9cpolar emollient,xe2x80x9d as used herein, means any emollient emulsifier having at least one polar moiety and wherein the solubility (at 30xc2x0 C.) of the vitamin B3 compound is in the polar emollient is greater than about 1.5%, preferably greater than about 2%, more preferably greater than about 3%. Suitable polar emollients include, but are not limited to, polyol ester and polyol ethers such as linear or branched chained polyglycerol esters and polyglycerol ethers. Nonlimiting examples of such emollients include PG3 diisosterate, polyglyceryl-2-sesquiisostearate, polyglyceryl-5-distearate, polyglyceryl-10-distearate, polyglyceryl-10-diisostearate, acetylated monoglycerides, glycerol esters, glycerol tricaprylate/caprate, glyceryl ricinoleate, glyceryl isostearate, glyceryl myristate, glyceryl linoleate, polyalkylene glycols such as PEG 600, monoglycerides, 2-monolaurin, sorbitan esters and mixtures thereof.
Also preferred are non-polar emollients. By xe2x80x9cnon-polar emollient,xe2x80x9d as used herein, means any emollient emulsifier possessing no permanent electric moments and wherein the solubility (at 30xc2x0 C.) of the vitamin B3 compound is in the polar emollient is less than about 1.5% preferably less than about 1.0%, more preferably less than about 0.5%. Suitable non-polar emollients include, but are not limited to, esters and linear or branched chained hydrocarbons. Nonlimiting examples of such emollients isononyl isononanioate, isopropyl isostearate, octyl hydroxystearate, diisopropyl dimerate, lanolin oil, octyl palmitate, isopropyl palmitate, paraffins, isoparrafins, acetylated lanolin, sucrose fatty acid esters, isopropyl myristate, isopropyl stearate, mineral oil, silicone oils, dimethicone, allantoin, isohexadecane, isododecane, petrolatum, and mixtures thereof.
The solubility of the vitamin B3 compound in polar or non-polar emollients is determined as set forth below.
Suitable oils include esters, triglycerides, hydrocarbons and silicones. These can be a single material or a mixture of one or more materials. They will normally comprise from 0% to about 100%, preferably from about 5% to about 90%, and most preferably from about 70% to about 90% of the emollient component.
Oils act as emollients and also impart viscosity, tackiness, and drag properties to cosmetic compositions such as lipsticks. Examples of suitable oils include caprylic triglycerides; capric triglyceride; isostearic triglyceride; adipic triglyceride; propylene glycol myristyl acetate; lanolin; lanolin oil; polybutene; isopropyl palmitate; isopropyl myristate; isopropyl isostearate; diethyl sebacate; diisopropyl adipate; tocopheryl acetate; tocopheryl linoleate; hexadecyl stearate; ethyl lactate; cetyl oleate; cetyl ricinoleate; oleyl alcohol; hexadecyl alcohol; octyl hydroxystearate; octyl dodecanol; wheat germ oil; hydrogenated vegetable oils; castor oil; petrolatum; modified lanolins; branched-chain hydrocarbons; alcohols and esters; corn oil; cottonseed oil; olive oil; palm kernel oil; rapeseed oil; safflower oil; jojoba oil; evening primrose oil; avocado oil mineral oil, sheabutter, octylpalimitate, maleated soybean oil, glycerol trioctanoate, diisopropyl dimerate, and volatile and non-volatile silicone oils including phenyl trimethicone.
The preferred oils for use herein are acetylglycerides, octanoates, and decanoates of alcohols and polyalcohols, such as those of glycol and glycerol, the ricinoleates of alcohols and polyalcohols such as cetyl ricinoleate, PG-3 diisostearate, polyglycerol ethers, polyglycerol esters, caprylic triglycerides, capric triglycerides, isostearic triglyceride, adipic triglyceride, phenyl trimethicone, lanolin oil, polybutene, isopropyl palmitate, isopropyl isostearate, cetyl ricinolcate, octyl dodecanol, oleyl alcohol, hydrogenated vegetable oils, castor oil, modified lanolins, octyl palmitate, lanolin oil, maleated soybean oil, cetyl ricinoleate, glyceryl trioctanoate, diisopropyl dimerate, synthetic lanolin derivatives and branched chain alcohols, sucrose esters of fatty acids, octyl hydroxystearate and mixtures thereof.
Preferably, the oils used are selected such that the majority (at least about 75%, preferably at least about 80% and most preferably at least about 99%) of the types of oils used have solubility parameters which do not differ by more than from about 1 to about 0.1, preferably from about 0.8 to about 0.1.
The emollient component comprises from about 1% to about 90%, preferably from about 10% to about 80%, more preferably from about 20% to about 70%, and most preferably from about 40% to about 60%, of the cosmetic composition.
Surfactants
Surfactants suitable for use are those which can form emulsions and/or association structures. Surfactant emulsifier can be from 0% to about 20% of the formulation, preferably from 0% to about 15% and most preferably from about 1% to about 10%. Examples of suitable emulsifiers can be found in U.S. Pat. No. 5,085,856 to Dunphy et al.; Japanese Patent Publication Sho 61-83110; European Patent Application EP 522624 to Dunphy et al.; U.S. Pat. No. 5,688,831 to El-Nokaly et al. Examples of other suitable emulsifiers can be found in Cosmetic Bench Reference, pp. 1.22, 1.24-1.26 (1996), all of which are herein incorporated by reference in their entirety.
Also useful herein are surfactants which form association structures, preferably lamellar or hexagonal liquid crystals, at ambient temperature when mixed with a polar solvent. Ambient temperature/room temperature as used herein typically means about 20xc2x0 C. Generally ambient temperature can range from about 18xc2x0 C. to about 27xc2x0 C. preferably from about 20xc2x0 C. to about 25xc2x0 C., depending on such variables as geographical location, i.e. sub-tropical vs. temperate regions. One of ordinary skill in the art is able to determine if association structures form at ambient temperatures. The surfactants suitable for use generally have a Krafft point at or below about ambient temperature about 20xc2x0 C. or generally at or below about 18xc2x0 C. to about 27xc2x0 C., preferably at or below from about 20xc2x0 C. to about 25xc2x0 C.
The definition of Krafft point is well known in the art and one of ordinary skill in the art can determine a surfactant""s Krafft point. In general terms, Krafft point is the melting point of the hydrocarbon chains of the surfactants. It can also be expressed as the temperature at which the solubility of an association colloid in water suddenly increases because critical micelle concentration is exceeded and micelles form. See Ekwall., P., xe2x80x9cComposition, Properties and Structure of Liquid Crystallitic IPhases in Systems of Amphiphiilic Compoundsxe2x80x9d Advances in Liquid Crystals Vol. I. Chapter 1. p.81.
In preparing a sample combination of surfactant and polar solvent to demonstrate the ability to form association structures, the surfactant needs to be sufficiently soluble in the polar solvent such that an association structure can form at ambient temperature. One of ordinary skill in the art is capable of determining compatible interactions.
Any surfactant which forms association structures at ambient temperature and is suitable for use in cosmetics is suitable for use herein. Surfactants suitable for use in cosmetics do not present dermatological or toxicological problems. Anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof are suitable for use. Preferably anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof having a Krafft point at or below about ambient temperature are used. More preferably, nonionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof having a Krafft point at or below about ambient temperature are used.
Surfactants suitable for use in forming association structures are found in U.S. Pat. No. 5,843,407 to El-Nokaly, herein incorporated by reference.
The association structures of the present invention are also useful in improving the skin penetration of the vitamin B3 compound. Without being limited by theory, the association structures are believed to act as occlusives oil the skin by forming continuous or discontinuous bi-layer or multi-layer films on the skin. The term xe2x80x9cocclusive,xe2x80x9d as used herein, means a preventing or obstructing something, in this case, preventing the removal of moisture (via evaporation) and the vitamin B3 compound (via film binding) from the surface of the skin. Furthermore, since the association structures of the present invention are thermodynamically stable, it is believed that the entrapped or bound polar solvent is slowly released over time. The slow release of the polar solvent thereby aids in maintaining the vitamin B3 compound in solubilized form, thus, improving skin penetration of the vitamin B3 compound. This occlusive effect is even further enhanced by the addition of the waxy or wax-like (or gel-like) solidifying agents disclosed above.
The surfactants can be used at levels from about 4% to about 97%, preferably from about 5% to about 95%, more preferably from about 20% to about 90% and most preferably from about 30% to about 70% of the association structure.
Solidifying Agent
The cosmetic compositions of this invention can contain one or more materials, herein singly or collectively referred to as a xe2x80x9csolidifying agentxe2x80x9d, that are effective to solidify the particular liquid base materials to be used in a cosmetic composition. (As used herein, the term xe2x80x9csolidifyxe2x80x9d refers to the physical and/or chemical alteration of the liquid base material so as to form a solid or semi-solid at ambient conditions, i.e., to form a final composition which has a stable physical structure and is deposited on the skin during normal use conditions.) As is appreciated by those skilled in the art, the selection of the particular solidifying agent for use in the cosmetic compositions will depend upon the particular type of composition desired, i.e., gel or wax-based, the desired rheology, the liquid base material used and the other materials to be used in the composition. The solidifying agent is preferably present at a concentration of from about 0 to about 90%, more preferably from about 1 to about 50%, even more preferably from about 5% to about 40%, most preferably from about 3% to about 20%.
The wax cosmetic stick embodiments of this invention preferably contain from about 5% to about 50% (by weight) of a waxy solidifying agent. By the term xe2x80x9cwaxy solidifying agent,xe2x80x9d as used herein, is meant a solidifying material having wax-like characteristics. Such waxy materials may also serve as emollients. Among the waxy materials useful herein are the high melting point waxes, i.e., having a melting point of from about 65xc2x0 C. to about 125xc2x0 C., such as beeswax, spermaceti, carnauba, baysberry, candelilla, montan, ozokerite, ceresin, paraffin, synthetic waxes such as Fishier-Tropsch waxes, microcrystalline wax, and mixtures thereof. Ceresin, ozokerite, white beeswax, synthetic waxes, and mixtures thereof, are among the preferred high-melting point waxes useful herein. Compositions containing waxes among those useful herein are disclosed in U.S. Pat. No. 4,049,792, Elsnau, issued Sep. 20, 1977, herein incorporated by reference in its entirety). Low melting waxes, having a melting point of from about 37xc2x0 C. to about 75xc2x0 C., are preferred for use in the wax stick embodiments of this invention. Wax stick embodiments of this invention, which contain volatile silicone oils as a liquid base material, preferably contain from about 10% to about 35%, more preferably from about 10% to about 20% (by weight), of a low-melting wax. Such materials include fatty acids, fatty alcohols, fatty acid esters and fatty acids amides, having fatty chains of from about 8 to about 30 carbon atoms, and mixtures thereof. Preferred wax-like materials include cetyl alcohol, palmitic acid, stearyl alcohol, behenamide, sucrose esters of tallow fatty acids, mono and di-fatty acid esters of polyethylene glycol, and mixtures thereof. Stearyl alcohol, cetyl alcohol, and mixtures thereof, are particularly preferred. Fatty acids, fatty alcohols, and other wax-like materials useful in this invention are also disclosed in the following refences, all of which are incorporated by reference herein: U.S. Pat. No. 4,151,272, Geary, et al., issued Apr. 24, 1979: U.S. Pat. No. 4,229,432, Geria, issued Oct. 21, 1980: and U.S. Pat. No. 4,280,994, Turney, issued July 28, 1981; xe2x80x9cThe Chemistry and Technology of Waxesxe2x80x9d, A. H. Warth, 2nd Edition, reprinted in 1960, Reinhold Publishing Corporation, pp 391-393 and 421: xe2x80x9cThe Petroleum Chemicals Industryxe2x80x9d, R. F. Goldstein and A. L. Waddeam, 3rd Edition (1967), E and F. N. Span Ltd., pp 33-40: xe2x80x9cThe Chemistry and Manufacture of Cosmeticsxe2x80x9d, M. G. DeNavarre, 2nd edition (1970), Van Nostrand and Company, pp 354-376; and in xe2x80x9cEncyclopedia of Chemical Technology:, Vol. 24, Kirk-Othmer, 3rd Edition (1979) pp 466-481. Preferred wax-like materials useful as solidifying agents in the present wax sticks are described in U.S. Pat. No. 4,126,679, Davy, et al., issued Nov. 21, 1978, herein incorporated by reference in its entirety. Preferred mixtures of wax-like materials comprise fatty alcohols containing carbon chains of from about 14 to about 18 carbon atoms, and alcohols having chain lengths of 20 carbons or longer, wherein the final mixture contains from about 1% to about 3% (by weight) of the longer-chain fatty alcohols. Compositions containing these fatty alcohol mixtures are described in European Patent Specification No. 117,070, May, published Aug. 29, 1984 (incorporated by reference herein).
Also useful herein are biopolymers such as those described in European Application No. 522624, to Dunphy et al., herein incorporated by reference in its entirety.
The gel stick embodiments of this invention preferably contain from about 3% to about 30%, preferably from about 3% to about 10% (by weight), of a solidifying agent. The particular amount of solidifying agent to be used will depend upon the particular solidifying agent and the liquid base material used, and the desired physical characteristics of the gel stick. Solidifying agents useful in the gel stick embodiments of this invention are, in general, surface-active compounds which form networks immobilizing or solidifying the liquid base materials into a gel. Such solidifying agents include: soaps, such as the sodium and potassium salts of higher fatty acids, i.e., acids having from 12 to 22 carbon atoms; amides of higher fatty acids; higher fatty acid amides of alkylolamines; dibenzaldehyde-monosorbitol acetals; alkali metal and alkaline earth metal salts of the acetates, propionates and lactates: waxes, such as candelilla and carnauba waxes; and mixtures thereof. Among those solidifying agents preferred for use in the gel stick embodiments of this invention are sodium stearate, sodium palmitate, aluminum stearate, aluminum magnesium hydroxy stearate, and mixtures thereof. Gel stick compositions containing solidifying agents among those useful herein are described in the following patent documents, all incorporated herein by reference in their entirety: U.S. Pat. No. 2,900,306, Slater, issued Aug. 18, 1959; U.S. Pat. No. 3,255,082, Barton, issued Jun. 7, 1966; U.S. Pat. No. 4,137,306, Rubino, et al., issued Jan. 30, 1979, U.S. Pat. No. 4,154,816, Roehl, et al., issued May 15, 1979; U.S. Pat. No. 4,226,889, Yuhas, issued Oct. 7, 1980; U.S. Pat. No. 4,346,079, Roehl, issued Aug. 24, 1982: U.S. Pat. No. 4,383,988, Teng, et al., issued May 17, 1983; European Patent Specification No. 107,330, Luebbe, et al., published May 2, 1984; and U.S. patent application Ser. No. 630,790. DiPietro, filed Jul. 13, 1984. Preferred solidifying agents useful in the gel stick embodiments of the present invention are described in European Patent Specification No. 24,365 Sampson. et al., published Mar. 4, 1981, incorporated herein by reference in its entirety.
Also useful herein as solidifying agents are conventional thickening agents. Examples of suitable thickeners include, but are not limited to naturally-occurring polymeric materials such as, locust bean gum, sodium alginate, sodium cascinate, egg albumin, gelatin agar, carrageenin gum sodium alginate, xanthan gum, quince seed extract, tragacanth gum, starch, chemically modified starches and the like, semi-synthetic polymeric materials such as cellulose ethers (e.g. hydroxyethyl cellulose, methyl cellulose, carboxylmethyl cellulose, hydroxy propylmethyl cellulose), polyvinylpyrrolidone, polyvinylalcohol, guar gum, hydroxypropyl guar gum, soluble starch, cationic celluloses, cationic guars and the like and synthetic polymeric materials such as carboxyvinyl polymers, polylvinylpyrrolidone, polyvinyl alcohol polyacrylic acid polymers, polymethacrylic acid polymers, polyvinyl acetate polymers, polyvinyl chloride polymers, polnvinylidene chloride polymers and the like. Inorganic thickeners may also be used such as aluminium silicates, such as, for example, bentonites, or a mixture of polyethylene glycol and polyethlylene glycol stearate or distearate. Naturally occurring polymers or biopolymers and their use are further described in European Application No. 5226224, to Dunphy et al. Additional examples of naturally occurring polymers or biopolymers can be found in the Cosmetic Bench Reference, pp. 1.40-1.42, herein incorporated by reference.
Also useful herein are hydrophilic gelling agents such as the acrylic acid/ethyl acrylate copolymers and the carboxyvinyl polymers sold by the B.F. Goodrich Company under the trademark of Carbopol Registered TM resins. These resins consist essentially of a colloidally water-soluble polyalkenyl polyether crosslinked polymer of acrylic acid crosslinked with from 0.75% to 2.00% of a crosslinking agent such as polyallyl sucrose or polyallyl pentaerythritol. Examples include Carbopol 934, Carbopol 940, Carbopol 950, Carbopol 980, Carbopol 951 and Carbopol 981. Carbopol 934 is a water-soluble polymer of acrylic acid crosslinked with about 1% of a polyallyl ether of sucrose having an average of about 5.8 allyl groups for each sucrose molecule. Also suitable for use herein are carbomers sold under the Trade Name xe2x80x9cCarbopol Ultrez 10, Carbopol ETD2020, Carbopol 1382, Carbopol 1342 and Pemulen TR-1 (CTFA Designation: Acrylates/10-30 Alkyl Acrylate Crosspolymer). Combination of the above polymers are also useful herein. Other gelling agents suitable for use herein include olcogels such as trihydroxystearin.
Hydrophobically modified celluloses are also suitable for use herein. These celluloses are described in detail in U.S. Pat. Nos. 4,228,277 and 5,104,646, both of which are herein incorporated by reference in their entirety.
Additional examples of suitable gelling agents or gellants can be found in the Cosmetic Bench Reference, p. 1.27, herein incorporated by reference.
Without being limited by theory, the solidifying agent in combination with the emollient is believed to act as an occlusive on the skin by forming continuous or discontinuous bi-layer or multi-layer films on the skin. The term xe2x80x9cocclusive,xe2x80x9d as used herein, means a preventing or obstructing something, in this case, preventing the removal of moisture (via evaporation) and the vitamin B3 compound (via film binding) from the surface of the skin.
Color
Certain embodiments of the present invention, preferably lipsticks or lip paints, contain from 0% to about 90%, preferably from about 1% to about 35%, more preferably from about 1% to about 20% and most preferably from about 5% to about 15%, of color, on an anhydrous pigment weight basis. These are usually aluminium, barium or calcium salts or lakes. Preferably, dyes are present at from about 0.1% to about 4% and pearls from 0% to about 20%.
Pigments are typically dispersed in emollients for the good dispersion of the pigments when incorporated into the lip compositions, thus providing an even distribution of color. Excellent dispersion of the pigment can be achieved by utilizing association structures, preferably lamellar liquid crystals, as a means of incorporating the color/pigments into the cosmetic compositions of the present invention. A preferred method of incorporating dry pigments comprises the steps of:
(a) preparing a mixture consisting essentially of:
(1) a polar solvent; and
(2) a surfactant selected from the group consisting of amphoteric, cationic, anionic and nonionic surfactants having a Krafft point at or below about ambient temperature and mixtures thereof; and
(b) stirring said mixture until association structures form;
(c) adding and mixing dry pigments until achieving a homogeneous mixture;
(d) milling said mixture until uniform particle size is achieved; and
(e) adding and mixing the mixture of (c) to the remaining ingredients until a homogenous mixture is obtained.
If the ingredients of the cosmetic composition are being processed such that the association structures are being formed in situ, the preferred method of incorporating the dry pigments is to slurry them in one or more of the liquid emollient ingredients.
Colors/pigments suitable for use herein are all inorganic and organic colors/pigments suitable for use in lipstick compositions.
Lakes are either a pigment that is extended or reduced with a solid diluent or an organic pigment that is prepared by the precipitation of a water-soluble dye on an adsorptive surface, which usually is aluminum hydrate. There is uncertainty in some instances as to whether the soluble dye precipitates on the surface of the aluminum hydrate to yield a dyed inorganic pigment or whether it merely precipitates in the presence of the substrate. A lake also forms from precipitation of an insoluble salt from an acid or basic dye. Calcium and barium lakes are also used herein.
Lakes suitable for use in the present invention include Red 3 Aluminum Lake, Red 21 Aluminiuim Lake, Red 27 Aluminum Lake, Red 28 Aluminum Lake, Red 33 Aluminum Lake, Yellow 5 Aluminum Lake, Yellow 6 Aluminum Lake, Yellow 10 Aluminum Lake, Orange 5 Aluminum Lake and Blue 1 Aluminum Lake, Red 6 Barium Lake, Red 7 Calcium Lake.
Other colors and pigments can also be included in the lipsticks, such as dyes and pearls, titanium oxides, Red 6, Red 21, Brown, Russet and Sienna dyes, chalk, talc, iron oxides and titanated micas.
Perferably, the color component is water-insoluble particulate solids having an average particle size diameter of less than about 5 microns, more preferably 2 microns, most preferably 1 micron.
Without being limited by theory, it is believed that such solid particulates position themselves at the interface of dispersed droplets (i.e., the discontinuous phase) and the continuous phase to serve as barriers, preventing the coalescence of the dispersed droplets and, hence, improving stabilization. A more detailed explanation of this phenomenon is described in S. E. Friberg and K{dot over (m)}re Larson, Food Emulsions, pp. 36-41, Marcel Dekker, Inc. (1997), herein incorporated by reference in its entirety.
Dispersants may also be used in conjunction with the colors and pigments of the present invention. Examples of suitable dispersants include, but are not limited to, those described in U.S. Pat. No. 5,688,493, herein incorporated by reference in its entirety.
Dermatogically Acccptable Cosmetic Carrier
The composition of the present invention in association with a cosmetically or dermatologically acceptable cosmetic vehicle or carrier. Such a carrier is compatible with the skin, the nails, the mucous membranes, tissues and the hair and includes any conventionally used cosmetic or dermatological carrier which meets these requirements. Such a carrier is also compatible with the vitamin B3 compound, that is the carrier should not interact with the vitamin B3 compound. Suitable carriers include, but are not limited to, solutions, soaps, bodywashes, emulsions, ointments, lipsticks, foundations, mascaras, powders, suspensions, creams, lotions, gels, foams, mousses and the like. These carriers facilitate topical application and, in some cases, provide additional therapeutic effects, e.g., by moisturizing of the affected skin areas. Dermatologically acceptable cosmetic carriers can be readily selected by one of ordinary skill in the art.
Other Additives
Other optional ingredients which can be present in the cosmetic compositions of the present invention include the flavor oils which were described above, fat soluble vitamins such as vitamin A and E, esters of vitamin A (e.g., acetate, propionate or palmitate) and of vitamin E (e.g., acetate or sorbate), sunscreens such as octyl methoxycinnamate and butyl methoxydibenzoylmethane, sunblocks such as titanium dioxide and zinc oxide, germicides such as triclosan, anti-inflammatory agents such as hydrocortisone, lipid materials such as ceramides and liposomes and skin care actives. The cosmetic compositions can comprise ingredients conventionally employed in cosmetic compositions such as mascara, foundation or lipcare products. This includes skin care active ingredients such as pharmaceutically active ingredients.
Skin care actives ingredients in both water soluble and water insoluble forms can be added to the cosmetic compositions of the present invention. These include, but are not limited to vitamin C and its derivatives (e.g., ascorbyl palmitate, ascorbyl phosphate and its salts such as magnesium or sodium), vitamin D, pathenol, retinoic acid, zinc oxide, beta-glycyerhetic acid; chamomile oil; ginko biloba extract; pyroglutamic acid, salts or esters; sodium hyaluronate; 2-hydroxyoctanoic acid; sulfur; salicylic acid; carboxmethyl cysteinie, and mixtures thereof.
These additives, both fat soluble and water soluble, will normally be present in amounts of less than about 10% by weight, and generally in the range of about 0.01% to about 5%, preferably from about 0.01% to about 3%, most preferably from about 0.1% to about 1%, by weight.
Flavor oils such as peppermint oil, orange oil, citris oil, wintergreen oil can be used along with an alcohol or glycerine. Flavor oils are usually mixed in a solvent such as ethanol to dilute the flavor. The flavor oils useful herein can be derived from natural sources or be synthetically prepared. Generally flavor oils are mixtures of ketones, alcohols, fatty acids, esters and terpenes. The term xe2x80x9cflavor oilxe2x80x9d is generally recognized in the art to be a liquid which is derived from botanical sources, i.e. leaves, bark, or skin of fruits or vegetables, and which are usually insoluble in water. The level of flavor oil used can range from 0% to about 5%, preferable from 0% to about 1%.
Moisturizers may also be included into the present compositions. Preferred moisturizers include pyrrolidone carboxylic acid, sodium lactate or lactic acid, urea, guanidine, glyceric acid and its salts (e.g., calcium salt), petrolatum, collagen, xcex1-hydroxy propylglyceryl ether, xcex1-hydroxy acids (e.g., ethylglycolic acid, leucic acid, mandelic acid, glycolic acid), glucosamines, and elastin fibers, D-panthenol, allantoin and hyaluronic acid and chondroitin sulfate. Examples of suitable moisturizers can be found in Cosmetic Bench Reference, p. 1.30-1.32 (1996), herein incorporated by reference.
A preferred optional component is ethyl cellulose (Ethocel). Ethyl cellulose generally is preferred for use at levels of about 5% and more preferably 1%.
Another preferred optional component is silica. Silica is generally preferred for use at levels of from about 1% and about 5%.
Hypoallergenic compositions can be made from the liquid crystal, wax, oil and colors herein. These compositions should not contain fragrances, flavor oils, lanolin, sunscreens, particularly PABA, or other sensitizers or potential sensitizers and irritants.
The compositions of the present invention can also be made into long lasting or non-transferable cosmetic compositions, Detailed discussions of such lipsticks are found in Japanese Patent Publication Hei No. 6-199630 and European Patent Application 748622, both of which are herein incorporated by reference in their entirety.
Additional optional materials that can be incorporated in the compositions of the present invention can be found in PCT application WO 97/39733, to Oblong et al.
The cosmetic compositions of the present invention are ideally suited for use in treating the skin and lips, especially in the form of a lipstick or lip balm for applying to the lips a permanent or semi-permanent color, ideally with a gloss or luster finish. The cosmetic compositions can also be used in treating the skin and/or lips with a skin care agent for protection against exposure to adverse weather, including the wind and the rain, dry and/or hot environments, environmental pollutants (e.g., ozone, smoke, and the like), or exposure to excessive doses of sunlight. The compositions are also useful in providing sun protection, moisturizing and/or conditioning for the hair and skin, improved skin feel, regulating skin texture, reducing fine lines and wrinkles, reducing oily shine on hair or skin, skin lightening and reducing skin or hair odor.
The cosmetic compositions can, accordingly, be applied to the skin and/or lips in the traditional manner with or without a convenient holder or applicator to provide a decorative and/or protective film thereto.
Methods of Determining Solubility of Vitamin B3 Compounds in Emollients
The solubility of the vitamin B3 compound in the various polar and non-polar emollients of the present invention can be determined as follows:
I. Preparation of Samples for Analysis:
1) the emollient is placed in pre-weighted vial and the saturated with a vitamin B3 compound;
2) the vial is shaken and allowed to sit in a bath at 30xc2x0 C. for 1 hour. A small stir bar is used to agitate the contents of the vial. If no precipitation occurs in the vial, then more niacinamide is added. This was repeated until precipitation occurred. The sample is left in the bath for an additional 48 hours to insure saturation;
3) the saturated emollient is drawn into a syringe;
4) A 0.45 micron filter (Gelman Acrodisc) is fitted on the end the syringe and the emollient is filtered through into separate pre-weighted vial for analysis;
5) The emollient is analyzed using HPLC to determine the amount of niacinamide therein.
II. Analysis:
Approximately 0.25 g of the sample is weighed (sample weight) into a 15 mL plastic screw-cap centrifuge tube. The sample is mixed with approximately 3 mL of 50/50 v/v methanol/chloroform and homogenized by vortex mixing. About 7 mL of water is then added to extract the vitamin B3 compound from the methanol/chloroform phase. Each sample is mixed by shaking 50 times in a back and forth motion to facilitate transfer of the niacinamide from the methanol/chloroform to the water phase. This mixing creates an emulsion at the interface of the two phases. The emulsion can be dissipated by letting the sample stand for several hours or by brief centrifugation (15 seconds) at high speed. Once the two phases have completely separated, a pipette is used to carefully transfer the aqueous phase into a separate, pre-weighted vial. The weight of the aqueous phase is noted (aqueous phase weight). An aliquot of the aqueous phase is transferred to an analysis container and analyzed for niacinamide by HPLC (Waters 2690 Separations Module coupled with a Waters 996 PDA detector, both supplied by Waters Corporations).
III. Calculations:
The percent vitamin B3 compound is determined by taking the vitamin B3 compound concentration measured by HPLC and multiplying by the dilution factor. The dilution factor is the aqueous phase weight divided by the sample weight.